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JP-7855473-B2 - Fluorene compounds, as well as their manufacturing methods and uses.

JP7855473B2JP 7855473 B2JP7855473 B2JP 7855473B2JP-7855473-B2

Inventors

  • 安田 理恵
  • 鞍谷 裕嗣
  • 沖見 克英

Assignees

  • 大阪ガスケミカル株式会社

Dates

Publication Date
20260508
Application Date
20220927

Claims (18)

  1. A compound represented by the following formula (1) or a salt thereof , [In the formula, R1 represents a substituent, and k1 represents an integer from 0 to 8.] Z1a and Z1b independently represent substituted or unsubstituted arene rings. Z2a and Z2b independently represent substituted or unsubstituted arene rings. A1a and A1b independently represent an alkylene group, and m1a and m1b independently represent an integer of 0 or more. R2a and R2b independently represent substituted or unsubstituted divalent hydrocarbon groups. R3a and R3b independently represent a hydroxyl group, a group [-OR h3 ] (wherein R h3 represents a hydrocarbon group), or a halogen atom. In formula (1) above, R1 is a halogen atom, a hydrocarbon group, a group [-OR h1 ] (wherein R h1 represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, or a substituted amino group, and k1 is an integer from 0 to 4. The arene rings of Z1a and Z1b are independently monocyclic or fused polycyclic arene rings. The arene rings of Z2a and Z2b are independently monocyclic or fused polycyclic arene rings. m1a and m1b are independent integers between 0 and 10. A compound or a salt thereof in which the divalent hydrocarbon groups R2a and R2b are independently alkylene groups.
  2. Crystals of the compound or a salt thereof according to claim 1 .
  3. A method for producing a compound represented by formula (1) or a salt thereof according to claim 1 , by reacting a compound represented by formula (2) or a salt thereof with a compound represented by formula (3a) and a compound represented by formula (3b) below. [In the formula, X1a and X1b , and X2a and X2b represent groups capable of forming a carbon-carbon bond with each other through a coupling reaction.] R1 , k1, Z1a and Z1b , Z2a and Z2b , A1a and A1b , m1a and m1b, R2a and R2b , R3a and R3b are the same as those in formula (1) above.
  4. A resin containing at least one constituent unit represented by the following formula (A-1). [In the formula, R1 , k1, Z1a and Z1b , Z2a and Z2b , A1a and A1b , m1a and m1b, and R2a and R2b are the same as those in formula (1) described in claim 1. ]
  5. The resin is a thermoplastic resin containing at least dicarboxylic acid units (A) derived from a dicarboxylic acid component as a polymerization component, The resin according to claim 4 , wherein the dicarboxylic acid unit (A) includes at least a constituent unit represented by formula (A-1) as the first dicarboxylic acid unit (A1).
  6. The resin according to claim 5 , wherein the dicarboxylic acid unit (A) further comprises at least a second dicarboxylic acid unit (A2) represented by the following formula (A-2). (In the formula, Z3 represents a substituted or unsubstituted arene ring.)
  7. The resin according to claim 6 , wherein in formula (A-2), the arene ring of Z3 is a condensed polycyclic arene ring.
  8. The resin according to claim 6 or 7 , wherein the ratio of the first dicarboxylic acid unit (A1) to the second dicarboxylic acid unit (A2) is the former/latter (molar ratio) = 10/90 to 90/10.
  9. The resin according to claim 5 , wherein the resin further comprises a polyester resin containing at least diol units (B) derived from a diol component as a polymerization component.
  10. The resin according to claim 9, wherein the diol unit (B) comprises at least one diol unit selected from a first diol unit (B1) represented by the following formula (B-1) and a second diol unit (B2) represented by the following formula (B -2 ). (In the formula, R4 represents a substituent, and k4 represents an integer from 0 to 8.) Z4a and Z4b independently represent substituted or unsubstituted arene rings. A2a and A2b independently represent linear or branched alkylene groups, and m2a and m2b independently represent 0 or an integer greater than or equal to 1. (In the formula, A3 represents a linear or branched alkylene group, and m3 represents an integer of 1 or more.)
  11. In the above formula (B-1), R4 is a halogen atom, a hydrocarbon group, an alkoxy group, an acyl group, a nitro group, a cyano group, or a substituted amino group, and k4 is an integer from 0 to 4. The arene rings of Z4a and Z4b are independently monocyclic or fused polycyclic arene rings. The resin according to claim 10 , wherein m2a and m2b are independently 0 to 10.
  12. The resin according to claim 10 or 11 , wherein the ratio of the first diol unit (B1) to the second diol unit (B2) is the former/latter (molar ratio) = 50/50 to 99/1.
  13. The dicarboxylic acid unit (A) further comprises at least a second dicarboxylic acid unit (A2) represented by formula (A-2) according to claim 6 , The resin according to claim 10 , wherein the diol unit (B) comprises at least the first diol unit (B1).
  14. A resin according to any one selected from claims 4 to 7 , 9 to 11 , and 13 , wherein the Abbe number νd is 17 to 23 and the partial dispersion ratio θgF is 0.67 or more.
  15. A method for producing the resin described in claim 4 , using the compound described in claim 1 or a salt thereof as a raw material.
  16. A molded article comprising the resin according to any one selected from claims 4 to 7 , 9 to 11 , and 13 .
  17. The molded article according to claim 16, which is an optical component.
  18. The molded article according to claim 16 , which is an optical lens.

Description

This invention relates to compounds (or salts thereof) having a 9,9-bisarylfluorene skeleton, derivatives thereof, and methods for producing the same, as well as their uses. Many small devices and mobile devices, such as smartphones and tablet PCs, are equipped with optical functions such as cameras in addition to image display capabilities. As these devices become more high-performance, the required characteristics of optical components are increasing. While many resin materials are used for optical components, offering advantages over optical glass in terms of lightness, impact resistance (flexibility), and moldability (productivity), existing resin materials may not always adequately meet the increasingly stringent requirements. For example, imaging lens units incorporated into devices with camera functionality are required to be miniaturized to accommodate the thinning and multi-functionality of the devices themselves, while simultaneously demanding higher resolution due to the increasing pixel count of image sensors. Therefore, various innovations are employed in the lens configuration, shape, and material selection of imaging lens units, resulting in optical designs that achieve compactness, high imaging performance, and correction of various aberrations. Generally, imaging lens units consist of multiple lenses with different Abbe numbers and refractive indices; for example, they are often composed of a combination of high-Abbe number and low-Abbe number lenses. However, the limited types of resin materials available for optical lenses restrict the design of diverse and highly effective lens units. Therefore, from the perspective of increasing design flexibility and achieving higher functionality or performance, expanding the range of material selection is considered crucial, and the development of various optical resin materials with different optical properties, such as Abbe number, is required. Furthermore, the partial dispersion ratio θgF is known as an index representing wavelength dispersion characteristics other than the Abbe number. Materials with a high partial dispersion ratio θgF (exhibiting large anomalous dispersion characteristics) can effectively correct or reduce chromatic aberration (shift in imaging position due to wavelength). Therefore, International Publication No. 2019/131258 (Patent Document 1), Japanese Patent Application Publication No. 2020-158723 (Patent Document 2), and International Publication No. 2017/146022 (Patent Document 3) propose resins or resin compositions exhibiting a high partial dispersion ratio θgF. Furthermore, Japanese Patent Publication No. 2009-256332 (Patent Document 4) and Japanese Patent Publication No. 2009-256333 (Patent Document 5) disclose specific carboxylic acids having a 9,9-bisarylfluorene skeleton. International Publication No. 2019/131258Japanese Patent Publication No. 2020-158723International Publication No. 2017/146022Japanese Patent Publication No. 2009-256332Japanese Patent Publication No. 2009-256333 [Compound represented by formula (1)] The present invention encompasses compounds (dicarboxylic acid compounds) (or salts thereof) represented by the following formula (1) and their derivatives. In this specification and in the claims, the compound represented by formula (1) may be simply referred to as "compound (1)". [In the formula, R1 represents a substituent, and k1 represents an integer from 0 to 8.] Z1a and Z1b independently represent substituted or unsubstituted arene rings. Z2a and Z2b independently represent substituted or unsubstituted arene rings. A1a and A1b independently represent an alkylene group, and m1a and m1b independently represent an integer of 0 or more. R2a and R2b independently represent substituted or unsubstituted divalent hydrocarbon groups. R 3a and R 3b independently represent a hydroxyl group, a group [-OR h3 ] (wherein R h3 represents a hydrocarbon group), or a halogen atom. In formula (1) above, the substituent represented by R 1 may be an inert, non-reactive group (or a non-polymerizable group) that is inert to the reaction, such as a halogen atom, a hydrocarbon group, a group [-OR h1 ] (wherein R h1 represents a hydrocarbon group), an acyl group, a nitro group, a cyano group, or a substituted amino group (mono or disubstituted amino group). Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Examples of alkyl groups (linear or branched alkyl groups) include C1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups, with C1-6 alkyl groups being preferred and C1-4 alkyl groups being even more preferred. Examples of cycloalkyl groups include C5-10 cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups. Examples of aryl groups include C6-12 aryl groups such as phenyl groups, alkylphenyl groups, biphenylyl groups, and naphthy